A number of process solutions for one-step synthesis of dimethyl ether (DME), including a step of its recovery from the gaseous and liquid phases, were reviewed. It was demonstrated that energy-intensive absorption is the most common method for DME recovery from a gaseous stream containing syngas components. It was also shown that the world licensors of one-step DME synthesis provide for an additional dehydration reactor to utilize the methanol co-product. Energy and capital intensity was estimated for two DME production options, specifically the methanol dehydration route and the one-step DME synthesis over a bifunctional catalyst. Finally, it was demonstrated that the one-step option is inferior to the two-step design in terms of both criteria, and that the key cost factor is associated with DME recovery from the gaseous phase.